JP2024523095A - Reagentless method for measuring and monitoring halide concentrations in electrodeposition solutions of iron triad metals and their alloys and process control - Google Patents

Abstract

Techniques are provided that include methods and apparatus for selectively measuring and monitoring halide concentrations in process solutions for iron triad metals and their alloys. The methods include monitoring halide ions based on a first analytical method, such as conductivity, with correction of a second analytical measurement of the concentration of an iron triad metal, such as nickel (Ni), as a result of a major metal concentration. From such measurements, the concentration of a particular halide ion can be selectively determined.

Description

The present disclosure relates to techniques for analysis and process control of processing solutions, such as semiconductor processing solutions, and for selective measurement and monitoring of halide concentrations in such processing solutions for iron triad metals and their alloys.

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63/209,128, filed June 10, 2021, and U.S. Provisional Patent Application No. 63/220,052, filed July 9, 2021, the contents of each of which are incorporated by reference in their entirety herein.

Processing solutions are used in several industries, including the semiconductor industry, to produce products with desirable properties. Such processing solutions may include iron triad metals, such as nickel (Ni) electrodeposits, which are widely used in the electronics, semiconductor, automotive, and other industries due to their suitable properties. For example, iron triad metals (e.g., nickel (Ni) electrodeposits) may have magnetic properties that can be altered by changing the ratio of different metal ions in the processing solution. Such iron triad metals, such as nickel (Ni) electrodeposits, may also have high chemical resistivity due to nickel oxide passivation layers, tunable stress levels, and high diffusion layer properties.

In the case of nickel (Ni) electrodeposits, the passivating properties of nickel (Ni) can reduce or prevent the use of nickel (Ni)-based anodes, for example in nickel sulfate (NiSO ₄ ) electrolytes. To counter such passivating properties, halide ions (e.g., chloride (Cl), bromide (Br), or iodide (I)) can be used to depassivate the nickel (Ni) surface and enable the anodic reaction (e.g., Ni + 6 halide (-) → Ni halide 6 (4-) + 2e (-)). Furthermore, halide ions can be consumed at the anode through side reactions (e.g., 2 halide (-) → halogen 2 + 2e (-)). Thus, halide ions in the process solution can be monitored and replenished as needed for consistent process performance.

Such measurements and monitoring may be performed, for example, by titration with silver nitrate (AgNO ₃ ). However, such methods require reagents, have relatively long processing times due to the need for multiple incremental additions of titrant, are relatively expensive due to the need for titrants containing silver (Ag) salts, and may have safety concerns due to the toxicity of silver (Ag). For example, safety issues may arise related to the need to extract samples for analysis and to perform waste disposal after analysis. Certain approaches may include drawbacks, such as potentiometric measurements using certain ion-selective electrodes, which require an additional dilution step for high concentrations. Other methodologies, such as ion chromatography and capillary electrophoresis, are both relatively expensive, difficult to automate, and may have relatively long analysis times.

U.S. Patent No. 6,458,262 U.S. Patent No. 6,673,226 US Patent Application Publication No. 2014/0158545 US Patent Application Publication No. 2013/0264214

It would therefore be desirable to provide a process and apparatus that provides economical, safe, efficient, relatively rapid and accurate selective measurement and monitoring of halide concentrations in processing solutions of iron triad metals and their alloys.

The present disclosure addresses these and other needs by providing techniques for selective measurement and monitoring of halide ions (e.g., chloride (Cl), bromide (Br), or iodide (I)) in process solutions, such as semiconductor process solutions.

An exemplary method is provided for determining a concentration of halide ions in a process solution containing a plurality of halide ions and one or more plating metals. The method includes performing a first analytical method to measure the conductivity of the process solution to provide a first measurement, performing a second analytical method to provide a second measurement, and determining a concentration of the halide ions based on the first and second measurements. The halide ions may be selected from a plurality of halide ions. The first analytical method may be different from the second analytical method.

In certain embodiments, the second analytical method may include measuring the concentration of one or more plating metals.

In certain embodiments, the concentration of one or more plating metals may be measured by UV-Vis (ultraviolet-visible spectroscopy).

In certain embodiments, the second analytical method may include measuring the absorbance of the treatment solution.

In certain embodiments, the plurality of halide ions may include chloride (Cl), bromide (Br), iodide (I), or a combination thereof.

In certain embodiments, the one or more plating metals may include iron triad metals and their alloys. In certain embodiments, the one or more plating metals may include nickel (Ni), cobalt (Co), or iron (Fe).

In certain embodiments, the treatment solution may include a mixture of one or more salts.

In certain embodiments, the conductivity of the treatment solution may be measured at a constant temperature.

In certain embodiments, the processing solution may be a semiconductor processing solution.

An exemplary method is provided for determining a concentration of a halide ion in a process solution containing a plurality of halide ions and a predetermined concentration of one or more plating metals. The method includes performing a first analytical method including measuring a conductivity of the process solution to provide a first measurement, and determining a concentration of the halide ion based on the first measurement and the predetermined concentration of the one or more plating metals. The halide ion is selected from a plurality of halide ions.

In certain embodiments, the plurality of halide ions may include chloride (Cl), bromide (Br), iodide (I), or a combination thereof.

In certain embodiments, the one or more plating metals may include iron triad metals and their alloys. In certain embodiments, the one or more plating metals may include nickel (Ni), cobalt (Co), or iron (Fe).

In certain embodiments, the treatment solution may include a mixture of one or more salts.

In certain embodiments, the conductivity of the treatment solution may be measured at a constant temperature.

In certain embodiments, the processing solution may be a semiconductor processing solution.

An exemplary apparatus is provided for determining a concentration of halide ions in a process solution containing a plurality of halide ions and one or more plating metals. The apparatus includes a reservoir adapted to contain a test solution including the process solution, and a sampling mechanism coupled to the reservoir and adapted to deliver a predetermined amount of the test solution from the reservoir to one or more sensors coupled to the sampling mechanism. Each of the one or more sensors is adapted to receive at least a portion of the predetermined amount of the test solution and is operative to perform one or more analytical methods. The one or more sensors are selected from the group consisting of a conductivity sensor and an absorbance sensor.

In certain embodiments, the test solution may include one or more samples of the process solution.

In certain embodiments, the test solution may further include one or more standard solutions.

In certain embodiments, the sampling mechanism may include a syringe, a volumetric flask, a graduated cylinder, a power injector, or a metering pump.

In certain embodiments, the one or more analytical methods may include measuring one or more of the conductivity of the test solution, the concentration of one or more plating metals, or the absorbance of the test solution.

In certain embodiments, the device may further include a spectrophotometer coupled to the absorbance sensor, a light source, a photodetector, or a combination thereof.

In certain embodiments, the device may further include a conductivity meter coupled to the conductivity sensor.

In certain embodiments, the one or more sensors may include a conductivity sensor and an absorbance sensor.

In certain embodiments, the process solution may include one or more plating metals at a predetermined concentration, and the one or more sensors may include a conductivity meter.

In certain embodiments, one or more plating metals may include iron triad metals and their alloys.

In certain embodiments, the one or more plating metals may include nickel (Ni), cobalt (Co), or iron (Fe).

1 illustrates a schematic diagram of an exemplary apparatus of the present disclosure for halide analysis of process solutions. 1 shows the results of measured chloride (Cl) concentration (g/L) versus expected chloride (Cl) concentration (g/L) in solution samples according to Example 1. 1 shows the results of measured chloride (Cl) concentration (g/L) versus expected chloride (Cl) concentration (g/L) in solution samples according to Example 2.

The present disclosure provides techniques for selective measurement and monitoring of halide ions (e.g., chloride (Cl), bromide (Br), or iodide (I)) in a process solution, such as a semiconductor process solution. In certain embodiments, the present disclosure combines a first analytical method with a second analytical method to accurately determine the concentration of a given halide ion in the solution. The first analytical method can be a conductivity measurement and the second analytical method can be an absorbance measurement. The present disclosure also provides for combining the first analytical method with a second analytical method, which can be, for example, a plating metal concentration in a process solution having a given concentration of a plating metal (e.g., nickel (Ni)) or a measurement of the same in the process solution. Thus, the halide ions present in the process solution can be selectively determined, measured, and monitored without reagents.

The technical terms used in this disclosure are generally known to those of skill in the art. As used herein, the phrase "predetermined concentration" refers to a known, target, or optimal concentration of a component in a solution.

As used herein, the terms "selective" or "selectively" refer to, for example, the monitoring, measurement, or determination of a characteristic of a particular or specific component. For example, selective measurement of halide ions refers to measuring one particular or predetermined halide ion of interest from among multiple halide ions present in a solution.

As used herein, the terms "accurate" or "precisely" refer to, for example, a measurement or determination that is relatively close or approximate to an existing or true value, a standard, or a known measurement or value.

As used herein, the terms "about" or "approximately" mean that a particular value, as determined by one of ordinary skill in the art, is within an acceptable range of error, which will depend in part on how the value is measured or determined, i.e., the limitations of the measurement system. For example, "about" can mean a range of up to 20%, up to 10%, up to 5%, and/or up to 1% of a given value.

As used herein, the terms "coupled" or "operably coupled" refer to one or more components that are combined with one another and, as used herein, are intended to mean either an indirect or direct connection. Thus, when a device couples to a second device, the connection may be by a direct connection or by an indirect mechanical or other connection through another device or connection.

The methods of the present disclosure may be applied to various types of solutions, including processing solutions. In certain embodiments, the processing solution may be a semiconductor processing solution.

In certain embodiments, the process solution may include one or more halide ions. One of ordinary skill in the art will appreciate that a wide variety of halide ions are suitable for use in the present disclosure. In certain embodiments, the one or more halide ions may include chloride (Cl), bromide (Br), iodide (I), or combinations thereof.

In certain embodiments, the treatment solution may include one or more plating metals. Those skilled in the art will appreciate that a wide variety of combinations of plating metals are suitable for use in the present disclosure. In certain embodiments, the one or more plating metals may include iron triad metals and alloys thereof. The iron triad metals may include nickel (Ni), cobalt (Co), and iron (Fe). In certain embodiments, the one or more plating metals may include nickel (Ni).

The methods of the present disclosure provide multiple analytical methods and measurements of the process solution to advantageously and selectively measure and monitor, for example, halide ions in the process solution. The concentration of one or more halide ions is monitored in the process solution, which may be performed by a first analytical method, for example, measuring the conductivity of the process solution. In certain aspects, the process solution may include a mixture of one or more salts (e.g., nickel sulfate and nickel chloride or nickel bromide, nickel sulfamate and nickel chloride or nickel bromide, or nickel chloride or nickel bromide and sodium chloride or sodium bromide). Those skilled in the art will appreciate that a wide variety of salts are suitable for use in the present disclosure.

In such an embodiment, a measurement of the conductivity of the process solution provides the total concentration of the salts. A second analytical measurement may be performed to selectively measure and monitor the halide ions (e.g., chloride (Cl) or bromide (Br)) in the process solution. In certain embodiments, the second analytical method may include measuring the plating metal concentration of the process solution, for example, one or more iron triad metals and alloys such as nickel (Ni). Those skilled in the art will appreciate that a wide variety of methods for measuring plating metal concentration are suitable for use in the present disclosure.

In certain embodiments, the second analytical method may include UV-Vis (ultraviolet-visible spectroscopy). Thus, information regarding the concentration of halides and plating metals in the process solution may be determined by an economical, safe, efficient, relatively fast and accurate method. These measurements may be used to selectively determine the concentration of halide ions in the process solution. In certain embodiments, the first analytical method, e.g., measuring the conductivity of the process solution, may be combined with a second analytical method, e.g., measuring the metal concentration of the process solution. In certain aspects, the calculation may be performed with an intermediate process that calculates the metal ion concentration.

For example, in certain embodiments, the halide ion concentration of the process solution may be determined as follows: [Halide] = A1 x [Conductivity] + B1 x [Metal] + C1. The coefficients (a), (b), and (c) may be determined by conductivity and spectroscopic measurements of several standard solutions containing known concentrations of metal and halide.

In certain embodiments, the concentration of halide ions in the process solution may be based on the raw analytical signal. For example, the concentration of one or more halides may be monitored in the process solution by performing a first analytical method, such as by measuring the conductivity of the process solution. A second analytical method may also be performed, such as by measuring the absorbance of the process solution. These measurements may be advantageously used to selectively determine the concentration of halide ions in the process solution.

For example, in certain embodiments, the halide ion concentration of a process solution may be determined as follows: [Halide] = A2 x [Conductivity] + B2 x [Absorbance] + C2. Coefficients (a), (b), and (c) may be determined by conductivity and spectroscopy measurements of solutions containing known concentrations of metals and halides.

These measurements may be used to selectively determine the concentration of halide ions in the process solution. In certain embodiments, a first analytical method, such as measuring the conductivity of the process solution, may be combined with a second analytical method, such as measuring the metal concentration of the process solution. Additionally, in certain embodiments, a first analytical method, such as measuring the conductivity of the process solution, may be combined with a second analytical method, such as measuring the absorbance of the process solution.

In certain embodiments, the conductivity of the process solution may be measured. For example, in certain embodiments, the conductivity of the process solution may be measured by a conductivity meter. Those skilled in the art will appreciate that a wide variety of methods for measuring conductivity are suitable for use in the present disclosure. In certain embodiments, the conductivity measurement may be performed at a constant temperature or temperature compensated. In certain embodiments, the conductivity measurement may be normalized to a particular temperature.

In certain embodiments, the absorbance of the process solution may be measured. Those skilled in the art will appreciate that a wide variety of methods for measuring absorbance are suitable for use in the present disclosure.

The disclosed method provides for selectively determining a concentration of a predetermined halide in a process solution. In certain embodiments, the method may include providing a process solution. The process solution may include a plurality of halides and a plating metal. In certain embodiments, a first analytical method may be performed on the process solution to provide a first measurement value. The first analytical method may include measuring the conductivity of the process solution. In certain embodiments, the method may include performing a second analytical method on the process solution to provide a second measurement value. The second analytical method may include measuring the concentration of the plating metal. The method may further include determining a concentration of the predetermined halide of the plurality of halides based on the first and second measurements.

The method of the present disclosure provides for selectively determining a concentration of a predetermined halide in a processing solution. In certain embodiments, the method may include providing a processing solution. The processing solution may include a plurality of halides and a plating metal. In certain embodiments, a first analytical method of the processing solution may be performed to provide a first measurement value. The first analytical method may include measuring the conductivity of the processing solution. In certain embodiments, the method may include performing a second analytical method of the processing solution to provide a second measurement value. The second analytical method may include measuring the absorbance of the processing solution. The method may further include determining a concentration of the predetermined halide of the plurality of halides based on the first and second measurements.

FIG. 1 illustrates a schematic of an exemplary apparatus of the present disclosure. In certain aspects, the exemplary apparatus may relate to measuring and monitoring halide concentrations in process solutions, for example, for iron triad metals and their alloys. The apparatus may include, for example, one or more sensors operative to perform one or more analytical methods. In certain embodiments, the one or more sensors may include a conductivity sensor 310, a light sensor 320 (e.g., an absorbance sensor), or a combination thereof. In certain embodiments, the apparatus may further include a conductivity meter 311, an absorbance meter 321, a light source 322, a light detector 323, or a combination thereof.

In certain embodiments, the conductivity meter 311 may be connected to the conductivity sensor 310. In certain embodiments, the absorbance meter 321, the light source 322, and/or the light detector 323 may be connected to the light sensor 320. In certain embodiments, the light source 322 and/or the light detector 323 may be connected to the absorbance meter 321. The apparatus may further include a selection device 100, a sample introduction device 200, or a combination thereof. In certain embodiments, the apparatus may further include a selection device 100 and a sample introduction device 200.

In certain embodiments, the selection device 100 may include a solution, such as one or more standard solutions, one or more processed samples, or a combination thereof. The selection device 100 may be coupled to a sample introduction device 200. In certain embodiments, the sample introduction device 200 may deliver a predetermined amount of the solution included in the selection device 100 to one or more sensors. In certain embodiments, the sample introduction device 200 may deliver about 5 mL to about 45 mL, about 5 mL to about 40 mL, about 5 mL to about 35 mL, about 5 mL to about 30 mL, about 5 mL to about 25 mL, about 5 mL to about 20 mL, about 5 mL to about 10 mL, or about 10 mL to about 30 mL of solution to one or more sensors. For example, the sampling introduction device may deliver about 5 mL, about 10 mL, about 15 mL, about 20 mL, about 25 mL, about 30 mL, about 35 mL, about 40 mL, or about 45 mL of solution to one or more sensors. A suitable sample introduction device 200 for delivering a predetermined amount of solution contained in the selection device 100 may include, for example, a syringe or graduated cylinder for manual delivery, or an automated syringe or metering pump with associated tubing and wiring for automated delivery. Delivery of the predetermined amount of solution may also be performed to a preset level detected by an automated level sensor. The selection device 100 may be a tank or reservoir. To automatically deliver the solution, the sample introduction device 200 may be connected to, for example, a pipe extending between the selection device 100 and one or more sensors, such as a conductivity sensor 310, an optical sensor 320, or a combination thereof.

In certain aspects, a first portion of the predetermined amount of solution may be delivered to a first sensor, e.g., a conductivity sensor 310, and a second portion of the predetermined amount of solution may be delivered to a second sensor, e.g., an optical sensor 320. In certain embodiments, the predetermined amount of solution may be delivered to one or more sensors arranged in series in any order, e.g., a first sensor followed by a second sensor. In certain embodiments, the predetermined portion of the solution may be delivered to one or more sensors arranged in combination with one another.

The one or more sensors may operate to perform one or more analytical methods. In certain embodiments, the one or more analytical methods may include measuring the conductivity (e.g., of a solution), measuring the concentration (e.g., of a plating metal in a solution), measuring the absorbance (e.g., of a solution), or a combination thereof. The one or more sensors may include a conductivity sensor 310, an optical sensor 320, or a combination thereof. In certain embodiments, the device may include a conductivity sensor 310 and an optical sensor 320. The conductivity sensor 310 may, for example, measure the conductivity of the solution. The optical sensor 320 may, for example, measure the absorbance of the solution. In certain aspects, the device may include a device or sensor for measuring, for example, the concentration of a plating metal in a solution. The one or more sensors may be in parallel, in series in any order, or in combination. For example, but not by way of limitation, in certain embodiments, the device may include a conductivity sensor 310 and an optical sensor 320 in parallel, in series in any order, or in combination. In certain embodiments, the conductivity sensor 310 and the optical sensor 320 may be in parallel.

In certain embodiments, the device may further include a conductivity meter 311. The conductivity meter 311 may be operably coupled to the conductivity sensor 310. In certain embodiments, the conductivity meter 311 may be operably coupled to the conductivity sensor 310 via a cable, e.g., an electrical cable. The device may further include a light absorbance meter 321, e.g., a spectrophotometer. In certain embodiments, the light absorbance meter 321 may be operably coupled to the light sensor 320. In certain aspects, the device may further include a light source 322, a light detector 323, or a combination thereof. In certain embodiments, the device may include a light source 322 and a light detector 323. The light source 322 may be operably coupled to the light absorbance meter 321 and/or the light sensor 320, e.g., by an optical fiber. The light detector 323 may be operably coupled to the light absorbance meter 321 and/or the light sensor 320, e.g., by an optical fiber.

After analytical measurements of the solution are completed, the solution can be either flowed back into the process or discharged as waste.

The subject matter disclosed herein may be better understood by reference to the following examples. The following examples are merely illustrative of the subject matter disclosed herein and should not be construed as limiting the scope of the subject matter in any way.

Example 1. Selective Measurement of Halide Ions Using Conductivity Measurements and Predetermined Nickel (Ni) Concentrations This example provides for the selective measurement of halide ions, e.g., chloride (Cl), in a process solution containing a predetermined concentration of nickel (Ni) using conductivity measurements and a predetermined concentration of plating metal. Conductivity was measured for six samples of process solutions containing plating metal (i.e., nickel (Ni)) and halide ions (i.e., chloride (Cl)) at predetermined nickel (Ni) concentrations. The results of the conductivity measurements for each sample are shown in Table 1 below.

The concentration of the halide ion, chloride (Cl), in each treatment solution sample was selectively determined from the measured conductivity values and the given concentration of the plating metal nickel (Ni) shown in Table 1.

The results are presented in Table 2 and Figure 2.

Calculation Parameters The following calculation parameters (Equation 1 and Table 3) were used to selectively determine the measured concentration of halide ions (i.e., chloride (Cl)) in the process solutions.
[Halide] = A1 x [Conductivity] + B1 x [Metal] + C1 (Equation 1)

Example 2: Selective Measurement of Halide Ions Using Conductivity and Absorbance Measurements This example provides for the selective measurement of halide ions, such as chloride (Cl), in a process solution using conductivity and absorbance measurements. Conductivity and absorbance were measured for five samples of process solutions containing plating metal (i.e., nickel (Ni)) and halide ions (i.e., chloride (Cl)). The expected nickel (Ni) and chloride (Cl) concentrations for each sample are shown in Table 4 below.

The conductivity and absorbance measurements for each sample are shown in Table 5 below. From the conductivity and absorbance measurements shown in Table 5, the concentration of the halide ion, chloride (Cl), in each treatment solution sample was selectively determined as shown in Table 5 and Figure 3.

Calculation Parameters The following calculation parameters (Equation 2 and Table 6) were used to selectively determine the measured concentrations of multiple bases in the mixed solution.
[Halide] = A2 × [Conductivity] + B2 × [Absorbance] + C2 (Equation 2)

Example 3. Selective Determination of Halide Ions (Chloride) - Qualitative Analysis The method disclosed herein was evaluated by qualitative analysis. A 30 point continuous run was performed with 3 point runs per day for 5 days. The results of the 30 point continuous run test are shown in Table 7 below.

The results of five days of testing, three points per day, are shown in Table 8 below.

The description herein merely illustrates the principles of the disclosed subject matter. Various modifications and alterations to the described embodiments will be apparent to those skilled in the art in view of the teachings herein. Accordingly, the disclosure herein is intended to illustrate, but not limit, the scope of the disclosed subject matter. Moreover, the principles of the disclosed subject matter may be implemented in various configurations and are not intended to be limited in any way to the specific embodiments presented herein.

In addition to the various embodiments shown and claimed, the disclosed subject matter also relates to other embodiments having other combinations of the features disclosed and claimed herein. Thus, the specific features presented herein may be combined with each other in other ways within the scope of the disclosed subject matter, such that the disclosed subject matter includes any suitable combination of the features disclosed herein. The foregoing description of specific embodiments of the disclosed subject matter has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosed subject matter to the disclosed embodiments.

It will be apparent to those skilled in the art that various modifications and variations can be made in the systems and methods of the disclosed subject matter without departing from the spirit or scope of the disclosed subject matter. Thus, it is intended that the disclosed subject matter includes modifications and variations that come within the scope of the appended claims and their equivalents.

Claims (28)

1. A method for determining a concentration of halide ions in a process solution containing a plurality of halide ions and one or more plating metals, comprising:
performing a first analytical method comprising measuring a conductivity of the process solution to provide a first measurement;
performing a second analytical method to provide a second measurement; and
determining a concentration of the halide ions based on the first measurement and the second measurement;
wherein said halide ion is selected from said plurality of halide ions;
wherein the first analytical method is different from the second analytical method;
Method. The method of claim 1, wherein the second analytical method includes measuring the concentration of the one or more plating metals. The method of claim 2, wherein the concentration of the one or more plating metals is measured by UV-Vis (ultraviolet-visible spectroscopy). The method of claim 1, wherein the second analysis method includes measuring the absorbance of the treatment solution. The method of claim 1, wherein the plurality of halide ions includes chloride (Cl), bromide (Br), iodide (I), or a combination thereof. The method of claim 1, wherein the one or more plating metals include iron triad metals and their alloys. The method of claim 6, wherein the one or more plating metals include nickel (Ni), cobalt (Co), or iron (Fe). The method of claim 6, wherein the treatment solution comprises a mixture of one or more salts. The method of claim 1, wherein the conductivity of the treatment solution is measured at a constant temperature. The method of claim 1, wherein the processing solution is a semiconductor processing solution. 1. A method for determining a concentration of halide ions in a process solution containing a plurality of halide ions and one or more plating metals at a predetermined concentration, comprising:
performing a first analytical method comprising measuring a conductivity of the process solution to provide a first measurement;
determining the concentration of the halide ions based on the first measurement and the predetermined concentration of the one or more plating metals;
wherein said halide ion is selected from said plurality of halide ions;
Method. The method of claim 11, wherein the plurality of halide ions includes chloride (Cl), bromide (Br), iodide (I), or a combination thereof. The method of claim 11, wherein the one or more plating metals include iron triad metals and their alloys. The method of claim 13, wherein the one or more plating metals include nickel (Ni), cobalt (Co), or iron (Fe). The method of claim 13, wherein the treatment solution comprises a mixture of one or more salts. The method of claim 11, wherein the conductivity of the treatment solution is measured at a constant temperature. The method of claim 11, wherein the processing solution is a semiconductor processing solution. 1. An apparatus for determining a concentration of halide ions in a process solution containing a plurality of halide ions and one or more plating metals, comprising:
a reservoir adapted to contain a test solution comprising the treatment solution;
a sampling mechanism coupled to the reservoir and adapted to deliver a predetermined volume of the test solution from the reservoir to one or more sensors coupled to the sampling mechanism;
wherein each of the one or more sensors is adapted to receive at least a portion of the volume of the test solution and is operative to perform one or more analytical methods;
wherein the one or more sensors are selected from the group consisting of a conductivity sensor and an absorbance sensor.
Device. The device of claim 18, wherein the test solution comprises one or more samples of the process solution. The device of claim 18, wherein the test solution further comprises one or more standard solutions. The apparatus of claim 18, wherein the sampling mechanism includes a syringe, a volumetric flask, a graduated cylinder, a power injector, or a metering pump. The device of claim 18, wherein the one or more analytical methods include measuring one or more of the conductivity of the test solution, the concentration of the one or more plating metals, or the absorbance of the test solution. The device of claim 18, further comprising a spectrophotometer, a light source, a photodetector, or a combination thereof coupled to the absorbance sensor. The apparatus of claim 18, further comprising a conductivity meter coupled to the conductivity sensor. The device of claim 18, wherein the one or more sensors include the conductivity sensor and the absorbance sensor. The apparatus of claim 18, wherein the process solution includes a predetermined concentration of the one or more plating metals, and the one or more sensors include the conductivity meter. The apparatus of claim 18, wherein the one or more plating metals include iron triad metals and alloys thereof. The apparatus of claim 27, wherein the one or more plating metals include nickel (Ni), cobalt (Co), or iron (Fe).